US20220081785A1 - Ambient air separation and soec front-end for ammonia synthesis gas production - Google Patents
Ambient air separation and soec front-end for ammonia synthesis gas production Download PDFInfo
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- US20220081785A1 US20220081785A1 US17/421,458 US202017421458A US2022081785A1 US 20220081785 A1 US20220081785 A1 US 20220081785A1 US 202017421458 A US202017421458 A US 202017421458A US 2022081785 A1 US2022081785 A1 US 2022081785A1
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 40
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 25
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 25
- 238000000926 separation method Methods 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title description 19
- 239000012080 ambient air Substances 0.000 title description 2
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012528 membrane Substances 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 2
- 229920005597 polymer membrane Polymers 0.000 claims description 2
- 239000003570 air Substances 0.000 description 46
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 238000011144 upstream manufacturing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000009620 Haber process Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 238000001991 steam methane reforming Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/27—Ammonia
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
- C25B1/042—Hydrogen or oxygen by electrolysis of water by electrolysis of steam
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Definitions
- the present invention relates to an improved process for generating synthesis gas for ammonia production.
- a typical ammonia-producing plant first converts a desulfurized hydrocarbon gas, such as natural gas (i.e. methane) or LPG (a liquefied petroleum gas, such as propane and butane) or petroleum naphtha into gaseous hydrogen by steam reforming. The hydrogen is then combined with nitrogen to produce ammonia via the Haber-Bosch process
- synthesis of ammonia requires a synthesis gas (syngas) comprising hydrogen (H 2 ) and nitrogen (N 2 ) in a suitable molar ratio of about 3:1.
- Ammonia is one of the most widely produced chemicals, and it is synthesized directly using gaseous hydrogen and nitrogen as reactants without precursors or by-products. In its gaseous state, nitrogen is largely available as N 2 , and it is normally produced by separating it from atmospheric air.
- the production of hydrogen (H 2 ) is still challenging and, for industrial synthesis of ammonia, it is most often obtained from steam methane reforming (SMR) of natural gas.
- SMR steam methane reforming
- N 2 is also introduced, thus rendering the need for an air separation unit superfluous, but a clean-up process is necessary to remove oxygen-containing species, such as O 2 , CO, CO 2 and H 2 O, in order to prevent the catalysts from being poisoned in the ammonia converter.
- Carbon dioxide is a product of SMR and can be separated and recovered inside the plant. Hydrogen production is therefore a critical process in ammonia synthesis, and a sustainable production of ammonia is desirable to reduce the consumption of a primary source, such as natural gas, and to avoid CO 2 emissions from the process.
- a primary source such as natural gas
- the air separation is ideally carried out by using a membrane or alternatively by using pressure swing adsorption (PSA) or temperature swing adsorption (TSA). This way, part of the oxygen is removed from the air and less oxygen needs to be burned and subsequently separated in the SOEC.
- PSA pressure swing adsorption
- TSA temperature swing adsorption
- PCT/EP2018/076616 allows for producing ammonia synthesis gas purely from sustainable resources. By combining this with partial air separation, an improved process integration can be achieved, as the oxygen in the air feed can be balanced to exactly match the required steam production in the SOEC layout combined with the ammonia loop. In addition, the upstream air separation reduces the content of other impurities in the air, especially CO 2 .
- the operating costs of the initial air separation step can be kept very low, as a high selectivity for oxygen rejection can be achieved in the separation step when the remaining oxygen content is left at say 15%, 10%, or even 5%, or potentially also down to 2%.
- the preparation of ammonia synthesis gas by electrolysis has been described in various patents and patent applications.
- a method for the anodic electrochemical synthesis of ammonia gas is described in US 2006/0049063.
- the method comprises providing an electrolyte between an anode and a cathode, oxidizing negatively charged nitrogen-contaming species and negatively charged hydrogen-containing species present in the electrolyte at the anode to form adsorbed nitrogen species and hydrogen species, respectively, and reacting the adsorbed nitrogen species with the adsorbed hydrogen species to form ammonia.
- ammonia is synthesized using electrochemical and non-electrochemical reactions.
- the electrochemical reactions occur in an electrolytic cell having a lithium ion-conductive membrane that divides the electrochemical cell into an anolyte compartment and a catholyte compartment, the latter including a porous cathode closely associated with the lithium ion-conductive membrane.
- WO 2008/154257 discloses a process for the production of ammonia that includes the production of nitrogen from the combustion of a stream of hydrogen mixed with air. Hydrogen used to produce the nitrogen for an ammonia combustion process may be generated from the electrolysis of water. Hydrogen produced by electrolysis of water may also be combined with nitrogen to produce ammonia.
- Frattini et al. (Renewable Energy 99 (2016), 472-482) describe a system approach in energy evaluation of different renewable energy sources integrated in ammonia production plants. The impact of three different strategies for renewables integration and scale-up sustainability in the ammonia synthesis process was investigated using thermochemical simulations. For a complete evaluation of the benefits of the overall system, the balance of plant, the use of additional units and the equivalent greenhouse gas emissions have been considered.
- Applicant's earlier patent application PCT/EP 2018/076616 concerns a method for generating ammonia synthesis gas by electrolysis, comprising feeding a mixture of steam and compressed air into the first of a series of electrolysis units and passing the outlet from one electrolysis unit to the inlet of the next electrolysis unit together with air.
- the electrolysis units are run in endothermal mode, and the nitrogen part of the synthesis gas is provided by burning the hydrogen produced by steam electrolysis by air in or between the electrolysis units.
- the electrolysis units are preferably solid oxide electrolysis cell (SOEC) stacks.
- the present invention provides a method for generating synthesis gas for ammonia production by electrolysis using SOEC stacks and a relatively small air separation step.
- the method avoids using an energy intensive air separation unit for high purity nitrogen production (cryogenic, pressure swing adsorption or the like) by taking advantage of the ability of being operated in an endothermal mode, and it provides the necessary nitrogen by burning the refined air from the relatively small air separation step with hydrogen produced by steam electrolysis to remove the residual air.
- the combustion of hydrogen and residual oxygen can take place inside the stacks or between separate stacks.
- the invention relates to a method for generating ammonia synthesis gas by electrolysis, said method comprising the steps of:
- the membrane unit is preferably a polymer membrane unit.
- a ceramic membrane, pressure swing adsorption (PSA) or temperature swing adsorption (TSA) can be used.
Abstract
In a method for generating ammonia synthesis gas by electrolysis, comprising the steps of compressing air and feeding it to an air separation process, in which the content of nitrogen is concentrated while the content of oxygen and CO2 is diluted, feeding a mixture of steam and the compressed and refined air into the electrolysis unit or into the first of a series of electrolysis units and passing the outlet from one electrolysis unit to the inlet of the next electrolysis unit, either together with air added after each electrolysis unit or only adding air after the last electrolysis unit, the electrolysis units are run in thermoneutral or endothermal mode and the nitrogen part of the synthesis gas is provided by burning the hydrogen produced by steam electrolysis by the refined air in or between the electrolysis units.
Description
- The present invention relates to an improved process for generating synthesis gas for ammonia production.
- A typical ammonia-producing plant first converts a desulfurized hydrocarbon gas, such as natural gas (i.e. methane) or LPG (a liquefied petroleum gas, such as propane and butane) or petroleum naphtha into gaseous hydrogen by steam reforming. The hydrogen is then combined with nitrogen to produce ammonia via the Haber-Bosch process
-
3 H2+N2→2 NH3 - Thus, the synthesis of ammonia (NH3) requires a synthesis gas (syngas) comprising hydrogen (H2) and nitrogen (N2) in a suitable molar ratio of about 3:1.
- Ammonia is one of the most widely produced chemicals, and it is synthesized directly using gaseous hydrogen and nitrogen as reactants without precursors or by-products. In its gaseous state, nitrogen is largely available as N2, and it is normally produced by separating it from atmospheric air. The production of hydrogen (H2) is still challenging and, for industrial synthesis of ammonia, it is most often obtained from steam methane reforming (SMR) of natural gas. Moreover, when air is used for reforming processes, N2 is also introduced, thus rendering the need for an air separation unit superfluous, but a clean-up process is necessary to remove oxygen-containing species, such as O2, CO, CO2 and H2O, in order to prevent the catalysts from being poisoned in the ammonia converter. Carbon dioxide is a product of SMR and can be separated and recovered inside the plant. Hydrogen production is therefore a critical process in ammonia synthesis, and a sustainable production of ammonia is desirable to reduce the consumption of a primary source, such as natural gas, and to avoid CO2 emissions from the process.
- In an earlier patent application by the Applicant (PCT/EP 2018/076616, now published as WO 2019/072608 A1), a process is described wherein synthesis gas for ammonia production is prepared by electrolysis using solid oxide electrolysis cell (SOEC) stacks without having to use air separation. That process uses a combination of water electrolysis and air combustion to facilitate high temperature electrolysis of steam, which effectively means that any oxygen in the water and air feed can be separated into a separate stream and an intermediate product of H2/N2 in a ratio which is suitable for ammonia production. The present invention can be seen as an enlarged embodiment of the process of PCT/EP2018/076616, in which the air fed to the SOEC stacks has gone through an air separation step upstream the SOEC stacks. The air separation is ideally carried out by using a membrane or alternatively by using pressure swing adsorption (PSA) or temperature swing adsorption (TSA). This way, part of the oxygen is removed from the air and less oxygen needs to be burned and subsequently separated in the SOEC.
- This allows for a smaller stack area in the SOEC and an improved process integration.
- The teaching of PCT/EP2018/076616 allows for producing ammonia synthesis gas purely from sustainable resources. By combining this with partial air separation, an improved process integration can be achieved, as the oxygen in the air feed can be balanced to exactly match the required steam production in the SOEC layout combined with the ammonia loop. In addition, the upstream air separation reduces the content of other impurities in the air, especially CO2.
- By only doing partial air separation, the operating costs of the initial air separation step can be kept very low, as a high selectivity for oxygen rejection can be achieved in the separation step when the remaining oxygen content is left at say 15%, 10%, or even 5%, or potentially also down to 2%.
- So far, the standard solution within this field has been to perform a two-step reforming front-end for an ammonia plant which is operated exclusively on fossil fuels.
- The preparation of ammonia synthesis gas by electrolysis has been described in various patents and patent applications. Thus, a method for the anodic electrochemical synthesis of ammonia gas is described in US 2006/0049063. The method comprises providing an electrolyte between an anode and a cathode, oxidizing negatively charged nitrogen-contaming species and negatively charged hydrogen-containing species present in the electrolyte at the anode to form adsorbed nitrogen species and hydrogen species, respectively, and reacting the adsorbed nitrogen species with the adsorbed hydrogen species to form ammonia.
- In US 2012/0241328, ammonia is synthesized using electrochemical and non-electrochemical reactions. The electrochemical reactions occur in an electrolytic cell having a lithium ion-conductive membrane that divides the electrochemical cell into an anolyte compartment and a catholyte compartment, the latter including a porous cathode closely associated with the lithium ion-conductive membrane.
- WO 2008/154257 discloses a process for the production of ammonia that includes the production of nitrogen from the combustion of a stream of hydrogen mixed with air. Hydrogen used to produce the nitrogen for an ammonia combustion process may be generated from the electrolysis of water. Hydrogen produced by electrolysis of water may also be combined with nitrogen to produce ammonia.
- So far, little attention has been paid to ammonia production using synthesis gas produced by electrolysis, especially generated using SOEC stacks. Recently, the design and analysis of a system for the production of “green” ammonia using electricity from renewable energy sources has been described (Applied Energy 192 (2017) 466-476). In this concept, solid oxide electrolysis (SOE) for hydrogen production is coupled with an improved Haber-Bosch reactor, and an air separator is included to supply pure nitrogen. An ammonia production with zero CO2 emission is said to be obtainable with a 40% power input reduction compared to equivalent plants.
- A flexible concept for the synthesis of ammonia from intermittently generated H2 is described (Chem. Ing. Tech. 86 No. 5 (2014), 649-657) and compared to the widely discussed power-to-gas concepts on a technical and economical level. The electrolytic synthesis of ammonia in molten salts under atmospheric pressure has been described (J. Am. Chem. Soc. 125 No. 2 (2003), 334-335), in which a new electrochemical method with high current efficiency and lower temperatures than in the Haber-Bosch process is used. In this method, nitride ion (N3-), produced by the reduction of nitrogen gas at the cathode, is anodically oxidized and reacts with hydrogen to produce ammonia at the anode.
- Frattini et al. (Renewable Energy 99 (2016), 472-482) describe a system approach in energy evaluation of different renewable energy sources integrated in ammonia production plants. The impact of three different strategies for renewables integration and scale-up sustainability in the ammonia synthesis process was investigated using thermochemical simulations. For a complete evaluation of the benefits of the overall system, the balance of plant, the use of additional units and the equivalent greenhouse gas emissions have been considered.
- Pfromm (J. Renewable Sustainable Energy 9 (2017), 034702) describes and sums up the most recent state of the art and especially the renewed interest in fossil-free ammonia production and possible alternatives to the Haber Bosch process.
- Wang et al. (AIChE Journal 63 No. 5 (2017), 1620-1637) deal with an ammonia-based energy storage system utilizing a pressurized reversible solid oxide fuel cell (R-SOFC) for power conversion, coupled with external ammonia synthesis and decomposition processes and a steam power cycle. Pure oxygen, produced as a side product in electrochemical water splitting, is used to drive the fuel cell.
- Applicant's earlier patent application PCT/EP 2018/076616, mentioned above, concerns a method for generating ammonia synthesis gas by electrolysis, comprising feeding a mixture of steam and compressed air into the first of a series of electrolysis units and passing the outlet from one electrolysis unit to the inlet of the next electrolysis unit together with air. The electrolysis units are run in endothermal mode, and the nitrogen part of the synthesis gas is provided by burning the hydrogen produced by steam electrolysis by air in or between the electrolysis units. The electrolysis units are preferably solid oxide electrolysis cell (SOEC) stacks.
- The method according to PCT/EP 2018/076616, however, allows for producing ammonia synthesis gas from sustainable resources only. Now it has turned out that, by combining this method with partial air separation, an improved process integration can be achieved as the oxygen in the air feed can be balanced to exactly match the required steam production in the SOEC layout combined with the ammonia loop. In addition, the upstream air separation reduces the content of other impurities in the air, especially CO2. So, reducing the content of CO2 upstream the SOEC allows for a simplification of the process layout, because a potential CO/CO2 removal upstream the ammonia loop then may be avoided, or at least it can be much simplified.
- So the present invention provides a method for generating synthesis gas for ammonia production by electrolysis using SOEC stacks and a relatively small air separation step. The method avoids using an energy intensive air separation unit for high purity nitrogen production (cryogenic, pressure swing adsorption or the like) by taking advantage of the ability of being operated in an endothermal mode, and it provides the necessary nitrogen by burning the refined air from the relatively small air separation step with hydrogen produced by steam electrolysis to remove the residual air. The combustion of hydrogen and residual oxygen can take place inside the stacks or between separate stacks.
- More specifically, the invention relates to a method for generating ammonia synthesis gas by electrolysis, said method comprising the steps of:
-
- compressing air and feeding it to an air separation process, in which the content of nitrogen is concentrated while the content of oxygen and CO2 is diluted,
- feeding a mixture of steam and the compressed and refined air into the electrolysis unit or into the first of a series of electrolysis units and
- passing the outlet from one electrolysis unit to the inlet of the next electrolysis unit, either together with air added after each electrolysis unit or only adding air after the last electrolysis unit,
wherein the electrolysis units are run in thermoneutral or endothermal mode and the nitrogen part of the synthesis gas is provided by burning the hydrogen produced by steam electrolysis by the refined air in or between the electrolysis units.
- The membrane unit is preferably a polymer membrane unit. Alternatively, a ceramic membrane, pressure swing adsorption (PSA) or temperature swing adsorption (TSA) can be used.
- The effect of using ambient air separation front-end using a membrane according to the invention is described in more detail in the following calculation examples.
- It has been verified that an air separation membrane installed front-end of the SOEC gives a good synergy. A simple calculation using compressed air on one side of a membrane and non-compressed air as sweep gas on the other side indicates that the oxygen concentration in the feed air can be reduced from 21% to 4.1%. The calculation is based on feed air (21% O2 and 79% N2 plus 400 ppm CO2) at 10 barg (10 kNm3/h) and a sweep gas (air, i.e. 21% O2 and 79% N2 plus 400 ppm CO2) at 0.5 barg (10 kNm3/h). The resulting feed air to the SOEC (6.7 kNm3/h) at 9 barg consists of 4.1% O2 and 95.9% N2.
- Since CO2 permeates approximately 30 times faster than N2, a membrane will be able to separate off CO2 effectively. At 30 bar, the calculation would look like this (dependent of the desired O2 concentration): Based on feed air (21% O2 and 79% N2 plus 400 ppm CO2) at 30 bar and a sweep gas (air, i.e. 21% O2 and 79% N2 plus 400 ppm CO2) at 0.5 bar, the resulting feed air to the SOEC at 30 bar would consist of 3.3% O2 and 96.6% N2 plus 20 ppm CO2.
Claims (3)
1. A method for generating ammonia synthesis gas by electrolysis, said method comprising the steps of:
compressing air and feeding it to an air separation process, in which the content of nitrogen is concentrated while the content of oxygen and CO2 is diluted,
feeding a mixture of steam and the compressed and refined air into the electrolysis unit or into the first of a series of electrolysis units and
passing the outlet from one electrolysis unit to the inlet of the next electrolysis unit, either together with air added after each electrolysis unit or only adding air after the last electrolysis unit,
wherein the electrolysis units are run in thermoneutral or endothermal mode and the nitrogen part of the synthesis gas is provided by burning the hydrogen produced by steam electrolysis by the refined air in or between the electrolysis units.
2. Method according to claim 1 , wherein the air separation process comprises a polymer membrane unit or a ceramic membrane.
3. Method according to claim 1 , wherein the air separation process comprises a pressure swing adsorption (PSA) unit or a temperature swing adsorption (TSA) unit.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DKPA201900424 | 2019-04-05 | ||
DKPA201900424 | 2019-04-05 | ||
PCT/EP2020/059119 WO2020201282A1 (en) | 2019-04-05 | 2020-03-31 | Ambient air separation and soec front-end for ammonia synthesis gas production |
Publications (1)
Publication Number | Publication Date |
---|---|
US20220081785A1 true US20220081785A1 (en) | 2022-03-17 |
Family
ID=70058396
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US17/421,458 Pending US20220081785A1 (en) | 2019-04-05 | 2020-03-31 | Ambient air separation and soec front-end for ammonia synthesis gas production |
Country Status (7)
Country | Link |
---|---|
US (1) | US20220081785A1 (en) |
EP (1) | EP3947780A1 (en) |
CN (1) | CN113423869A (en) |
AR (1) | AR118564A1 (en) |
AU (1) | AU2020254955A1 (en) |
CL (1) | CL2021002472A1 (en) |
WO (1) | WO2020201282A1 (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US1386760A (en) * | 1912-09-14 | 1921-08-09 | Chemical Foundation Inc | Process and means relating to the production of ammonia |
US5348592A (en) * | 1993-02-01 | 1994-09-20 | Air Products And Chemicals, Inc. | Method of producing nitrogen-hydrogen atmospheres for metals processing |
US20080311022A1 (en) * | 2007-06-14 | 2008-12-18 | Battelle Energy Alliance, Llc | Methods and apparatuses for ammonia production |
US8623313B2 (en) * | 2009-01-09 | 2014-01-07 | Toyota Jidosha Kabushiki Kaisha | Ammonia synthesis process |
US20150004510A1 (en) * | 2012-01-09 | 2015-01-01 | Commissariat A L'energie Atomique Et Aux Ene Alt | High temperature steam electrolysis facility (htse) with allothermal hydrogen production |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7314544B2 (en) | 2004-09-07 | 2008-01-01 | Lynntech, Inc. | Electrochemical synthesis of ammonia |
EP2688841B1 (en) | 2011-03-23 | 2016-01-06 | Ceramatec, Inc | Ammonia synthesis using lithium ion conductive membrane |
EP2589426B1 (en) * | 2011-11-02 | 2016-06-08 | Casale Sa | Method for removing nitrogen oxides from combustion fumes with on-site generation of ammonia |
CN105836759A (en) * | 2016-05-04 | 2016-08-10 | 陈志强 | Ammonia carbon-free synthesis system by means of nuclear energy and method thereof |
AU2016101434A4 (en) * | 2016-08-10 | 2016-09-08 | Cooper, James MR | High Temperature Electrolysis plus Haber Bosch for Renewable Ammonia Exports |
UA126930C2 (en) | 2017-10-11 | 2023-02-22 | Хальдор Топсьое А/С | A method for generating synthesis gas for ammonia production |
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2020
- 2020-03-31 CN CN202080013928.7A patent/CN113423869A/en active Pending
- 2020-03-31 AU AU2020254955A patent/AU2020254955A1/en active Pending
- 2020-03-31 US US17/421,458 patent/US20220081785A1/en active Pending
- 2020-03-31 WO PCT/EP2020/059119 patent/WO2020201282A1/en unknown
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AR118564A1 (en) | 2021-10-20 |
CL2021002472A1 (en) | 2022-06-24 |
WO2020201282A1 (en) | 2020-10-08 |
CN113423869A (en) | 2021-09-21 |
AU2020254955A1 (en) | 2021-07-29 |
EP3947780A1 (en) | 2022-02-09 |
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